Pressure-Induced Distinct Self-Trapped Exciton Emission in Sb^(3+)-Doped Cs_(2)NaInCl_(6)Double Perovskite

The Cs_(2)NaInCl_(6) double perovskite is one of the most promising lead-free perovskites due to its exceptional stability and straightforward synthesis.However,it faces challenges related to inefficient photoluminescence.Doping and high pressure are employed to tailor the optical properties of Cs_(2)NaInCl_(6).Herein,Sb^(3+)doped Cs_(2)NaInCl_(6)(Sb^(3+):Cs_(2)NaInCl_(6)) was synthesized and it exhibits blue emission with a photoluminescence quantum yield of up to 37.3%.Further,by employing pressure tuning,a blue stable emission under a very wide range from 2.7 GPa to 9.8 GPa is realized in Sb^(3+):Cs_(2)NaInCl_(6).Subsequently,the emission intensity of Sb^(3+):Cs_(2)NaInCl_(6) experiences a significant increase(3.3 times)at 19.0 GPa.It is revealed that the pressure-induced distinct emissions can be attributed to the carrier self-trapping and detrapping between Cs_(2)NaInCl_(6) and Sb^(3+).Notably,the lattice compression in the cubic phase inevitably modifies the band gap of Sb^(3+):Cs_(2)NaInCl_(6).Our findings provide valuable insights into effects of the high pressure in further boosting unique emission characteristics but also offer promising opportunities for development of doped double perovskites with enhanced optical functionalities.

First-Principles Calculations on Novel Rb-Based Halide Double Perovskites Alloys for Spintronics and Optoelectronic Applications

The outcomes of computational study of electronic, magnetic and optical spectra for A2BX6 (A = Rb;B = Tc, Pb, Pt, Sn, W, Ir, Ta, Sb, Te, Se, Mo, Mn, Ti, Zr and X = Cl, Br) materials have been proceeded utilizing Vanderbilt Ultra Soft Pseudo Potential (US-PP) process. The Rb2PbBr6 and Rb2PbCl6 are found to be a (Г-Г) semiconductors with energy gaps of 0.275 and 1.142 eV, respectively making them promising photovoltaic materials. The metallic behavior of the materials for Rb2BX6 (B = Tc, W, Ir, Ta, Mn, Sb, Mo) has been confirmed showing the attendance of conducting lineaments. The dielectric function is found to be large close to the ultraviolet districts (3.10 - 4.13 eV). The extinction coefficient of the Rb2BX6 has the ability to be used for implements. The band structures and density of states ensure the magnetic semiconductors’ nature of the Rb2Mn (Cl, Br)6 perovskites. The total calculated magnetic moment of Rb2MnCl6 and Rb2MnB6 is 3.00μβ. Advanced spintronic technology requires room-temperature ferromagnetism. The present work confirms that, bromine and chlorine-founded double perovskites are extremely attractive for photovoltaic and optoelectronic devices.

Alternative lead-free mixed-valence double perovskites for high-efficiency photovoltaic applications

Lead-based organic-inorganic hybrid perovskites have exhibited great potential in photovoltaics,achieving power conversion efficiencies(PCEs) exceeding 25%.However,the toxicity of lead and the instability of these materials under moist conditions pose significant barriers to large-scale production.To overcome these limitations,researchers have proposed mixed-valence double perovskites,where Cs_(2)Au~ⅠAu~ⅢI_6 is a particularly effective absorber due to its suitable band gap and high absorptance efficiency.To further extend the scope of these lead-free materials,we varied the trivalent gold ion and halogen anion in Cs_(2)Au~ⅠAu~ⅢI_6,resulting in 18 new structures with unique properties.Further,using first-principles calculations and elimination criteria,we identified four materials with ideal band gaps,small effective carrier mass,and strong anisotropic optical properties.According to theoretical modeling,Cs_(2)AuSbCl_6,Cs_(2)AuInCl_6,and Cs_(2)AuBiCl_6 are potential candidates for solar cell absorbers,with a spectroscopic limited maximum efficiency(SLME) of approximately 30% in a 0.25 μm-thick film.These three compounds have not been previously reported,and therefore,our work provides new insights into potential materials for solar energy conversion.We aim for this theoretical exploration of novel perovskites to guide future experiments and accelerate the development of high-performance photovoltaic devices.

First Principle Study of Cesium-based Lead-free Halide Double Perovskites

Inorganic halide double perovskites A_(2)B'B"X_(6) have gained significant interests for their diverse composition,stable physicochemical properties,and potential for photoelectric applications.The influences of trivalent and monovalent cations on the formation energy,decomposition energy,electronic structure and optical properties of cesium-based lead-free Cs^(+)_(2)B'B"Br_(6) (B'=Na^(+),In^(+)Cu^(+),or Ag^(+);B"=Bi^(3),Sb^(3+),In^(3+)) are systematically studied.In view of the analysis and results of the selected double perovskites,for the double perovskites with different B-site trivalent cation,the band gap increases in the order of Cs_(2)AgInBr_(6),Cs_(2)AgSbBr_(6) and Cs_(2)AgBiBr_(6),with Cs_(2)AgBiBr_(6) possessing the highest thermodynamic stability.Therefore,the Bi-based perovskites are further studied to elucidate the effect of monovalent cation on their stability and electronics.Results show that the thermodynamic stability rises in the sequence of Cs_(2)NaBiBr_(6),Cs_(2)InBiBr_(6),Cs_(2)AgBiBr_(6) and Cs_(2)CuBiBr_(6).Notably,Cs_(2)CuBiBr_(6) exhibits a relatively narrow and appropriate band gap of 1.4634 eV,together with the highest absorption coefficient than other compounds,suggesting that Cs_(2)CuBiBr_(6) is a promising light absorbing material that can be further explored experimentally and be applied to optoelectronic devices.Our research offers theoretical backing for the potential optoelectronic application of cesium-based lead-free halide double perovskites in solar energy conversion.

Double Layer Composite Electrode Strategy for Efficient Perovskite Solar Cells with Excellent Reverse-Bias Stability

Perovskite solar cells(PSCs)have become the represent-atives of next generation of photovoltaics;nevertheless,their stability is insufficient for large scale deployment,particularly the reverse bias stability.Here,we propose a transparent conducting oxide(TCO)and low-cost metal composite electrode to improve the stability of PSCs without sacrificing the efficiency.The TCO can block ion migrations and chemical reactions between the metal and perovskite,while the metal greatly enhances the conductivity of the composite electrode.As a result,composite electrode-PSCs achieved a power conversion efficiency(PCE)of 23.7%(certified 23.2%)and exhibited excellent stability,maintaining 95%of the initial PCE when applying a reverse bias of 4.0 V for 60 s and over 92%of the initial PCE after 1000 h continuous light soaking.This composite electrode strategy can be extended to different combinations of TCOs and metals.It opens a new avenue for improving the stability of PSCs.

Simultaneous bottom-up double-layer synergistic engineering by multifunctional natural molecules for efficient and stable SnO2-based planar perovskite solar cells

The performance and stability of perovskite solar cells(PSCs)is limited by detrimental defects,mostly distributed at the grain boundary(GB)of bulk perovskite film and interface,which induce serious carrier non-radiative recombination.Therefore,there is particularly urgent to realize simultaneous passivation of bulk defects and interfacial defects.In this work,a simple,low-cost and effective multifunctional modification strategy is developed by introducing theλ-Carrageenan(λ-C)as the interfacial layer of SnO_(2)/perovskite.The sulfate groups ofλ-C not only play a positive role in passivating the Sn4+from SnO_(2)film,resulting in high conductivity,but also effectively passivate the defects at the SnO_(2)/perovskite interface.Meanwhile,λ-C can effectively passivate the defects in the perovskite film due to the strong binding force between the high content of sulfate groups and PbI2.The synergistic effect ofλ-C simultaneously achieves interfacial defects and bulk defects passivation,better crystalline quality,suppressed charge recombination,released interfacial stress and more favorable interfacial energy level alignment.Based on the above efficient synergy,theλ-C-modified device achieves a high efficiency of 23.81%,which is~24.53%higher than the control device(19.12%).To our best knowledge,23.81%of power conversion efficiency(PCE)is the highest reported PCE value of PSCs employing green natural additives.Moreover,long-term and thermal stabilities are significantly improved after interface modification.Thus,this work provides an idea for developing multifunctional natural materials towards the attainment of the efficient and stable PSCs.

基于softmax的加权Double Q-Learning算法

强化学习作为机器学习的一个分支,用于描述和解决智能体在与环境的交互过程中,通过学习策略以达成回报最大化的问题。Q-Learning作为无模型强化学习的经典方法,存在过估计引起的最大化偏差问题,并且在环境中奖励存在噪声时表现不佳。Double Q-Learning(DQL)的出现解决了过估计问题,但同时造成了低估问题。为解决以上算法的高低估问题,提出了基于softmax的加权Q-Learning算法,并将其与DQL相结合,提出了一种新的基于softmax的加权Double Q-Learning算法(WDQL-Softmax)。该算法基于加权双估计器的构造,对样本期望值进行softmax操作得到权重,使用权重估计动作价值,有效平衡对动作价值的高估和低估问题,使估计值更加接近理论值。实验结果表明,在离散动作空间中,相比于Q-Learning算法、DQL算法和WDQL算法,WDQL-Softmax算法的收敛速度更快且估计值与理论值的误差更小。

基于Dueling Double DQN的交通信号控制方法

为了提高交叉口通行效率缓解交通拥堵,深入挖掘交通状态信息中所包含的深层次隐含特征信息,提出了一种基于Dueling Double DQN(D3QN)的单交叉口交通信号控制方法;构建了一个基于深度强化学习Double DQN(DDQN)的交通信号控制模型,对动作-价值函数的估计值和目标值迭代运算过程进行了优化,克服基于深度强化学习DQN的交通信号控制模型存在收敛速度慢的问题;设计了一个新的Dueling Network解耦交通状态和相位动作的价值,增强Double DQN(DDQN)提取深层次特征信息的能力;基于微观仿真平台SUMO搭建了一个单交叉口模拟仿真框架和环境,开展仿真测试;仿真测试结果表明,与传统交通信号控制方法和基于深度强化学习DQN的交通信号控制方法相比,所提方法能够有效减少车辆平均等待时间、车辆平均排队长度和车辆平均停车次数,明显提升交叉口通行效率。

Microwave shock motivating the Sr substitution of 2D porous GdFeO_(3) perovskite for highly active oxygen evolution

The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.

High performance wide bandgap perovskite solar cell with low V_(OC) deficit less than 0.4 V

Wide bandgap perovskite solar cells(PSCs)have attracted significant attention because they can be applied to the top cells of tandem solar cells.However,high open-circuit voltage(V_(OC))deficit(>0.4 V)result from poor crystallization and high non-radiative recombination losses become a serious limitation in the pursuit of high performance.Here,the relevance between different Pbl_(2)proportions and performance parameters are revealed through analysis of surface morphology,residual stress,and photostability.The increase of Pbl_(2)proportion promotes crystal growth and reduces the work function of the perovskite film surface and promotes the energy level alignment with the carrier transport layer,which decreased the V_(OC)deficit.However,residual PbI_(2)exacerbated the stress level of perovskite film,and the resulting lattice disorder deteriorated the photostability of the device.Ultimately,after the synergistic passivation of residual PbI_(2)and PEAI,the V_(OC)achieves 1.266 V and V_(OC)deficit is less than 0.4 V,the record value in wide bandgap PSCs.

Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.

Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.

Constructing low-dimensional perovskite network to assist efficient and stable perovskite solar cells

The use of low-dimensional(LD)perovskite materials is crucial for achieving high-performance perovskite solar cells(PSCs).However,LD perovskite films fabricated by conventional approaches give rise to full coverage of the underlying 3D perovskite films,which inevitably hinders the transport of charge carriers at the interface of PSCs.Here,we designed and fabricated LD perovskite structure that forms net-like morphology on top of the underlying three-dimensional(3D)perovskite bulk film.The net-like LD perovskite not only reduced the surface defects of 3D perovskite film,but also provided channels for the vertical transport of charge carriers,effectively enhancing the interfacial charge transfer at the LD/3D hetero-interface.The net-like morphological design comprising LD perovskite effectively resolves the contradiction between interfacial defect passivation and carrier extraction across the hetero-interfaces.Furthermore,the net-like LD perovskite morphology can enhance the stability of the underlying 3D perovskite film,which is attributed to the hydrophobic nature of LD perovskite.As a result,the net-like LD perovskite film morphology assists PSCs in achieving an excellent power conversion efficiency of up to 24.6%with over 1000 h long-term operational stability.

Stabilizing perovskite precursors with the reductive natural amino acid for printable mesoscopic perovskite solar cells

Solution processability significantly advances the development of highly-efficient perovskite solar cells.However,the precursor solution tends to undergo irreversible degradation reactions,impairing the device performance and reproducibility.Here,we utilize a reductive natural amino acid,Nacetylcysteine(NALC),to stabilize the precursor solution for printable carbon-based hole-conductorfree mesoscopic perovskite solar cells.We find that I_(2) can be generated in the aged solution containing methylammonium iodide(MI) in an inert atmosphere and speed up the MA-FA^(+)(formamidinium) reaction which produces large-size cations and hinders the formation of perovskite phase.NALC effectively stabilizes the precursor via its sulfhydryl group which reduces I_(2) back to I^(-)and provides H^(+).The NALC-stabilized precursor which is aged for 1440 h leads to devices with a power conversion efficiency equivalent to 98% of that for devices prepared with the fresh precursor.Furthermore,NALC improves the device power conversion efficiency from 16.16% to 18.41% along with enhanced stability under atmospheric conditions by modifying grain boundaries in perovskite films and reducing associated defects.

Boosting MA-based two-dimensional Ruddlesden-Popper perovskite solar cells by incorporating a binary spacer

Two-dimensional Ruddlesden-Popper(2DRP)perovskite exhibits excellent stability in perovskite solar cells(PSCs)due to introducing hydrophobic long-chain organic spacers.However,the poor charge transporting property of bulky organic cation spacers limits the performance of 2DRP PSCs.Inspired by the Asite cation alloying strategy in 3D perovskites,2DRP perovskites with a binary spacer can promote charge transporting compared to the unary spacer counterparts.Herein,the superior MA-based 2DRP perovskite films with a binary spacer,including 3-guanidinopropanoic acid(GPA)and 4-fluorophenethylamine(FPEA)are realized.These films(GPA_(0.85)FPEA_(0.15))_(2)MA_(4)Pb_5I_(16)show good morphology,large grain size,decreased trap state density,and preferential orientation of the as-prepared film.Accordingly,the present 2DRP-based PSC with the binary spacer achieves a remarkable efficiency of 18.37%with a V_(OC)of1.15 V,a J_(SC)of 20.13 mA cm^(-2),and an FF of 79.23%.To our knowledge,the PCE value should be the highest for binary spacer MA-based 2DRP(n≤5)PSCs to date.Importantly,owing to the hydrophobic fluorine group of FPEA and the enhanced interlayer interaction by FPEA,the unencapsulated 2DRP PSCs based on binary spacers exhibit much excellent humidity stability and thermal stability than the unary spacer counterparts.

Efficient and Stable Inverted Perovskite Solar Modules Enabled by Solid-Liquid Two-Step Film Formation

A considerable efficiency gap exists between large-area perovskite solar modules and small-area perovskite solar cells.The control of forming uniform and large-area film and perovskite crystallization is still the main obstacle restricting the efficiency of PSMs.In this work,we adopted a solid-liquid two-step film formation technique,which involved the evaporation of a lead iodide film and blade coating of an organic ammonium halide solution to prepare perovskite films.This method possesses the advantages of integrating vapor deposition and solution methods,which could apply to substrates with different roughness and avoid using toxic solvents to achieve a more uniform,large-area perovskite film.Furthermore,modification of the NiO_(x)/perovskite buried interface and introduction of Urea additives were utilized to reduce interface recombination and regulate perovskite crystallization.As a result,a large-area perovskite film possessing larger grains,fewer pinholes,and reduced defects could be achieved.The inverted PSM with an active area of 61.56 cm^(2)(10×10 cm^(2)substrate)achieved a champion power conversion efficiency of 20.56%and significantly improved stability.This method suggests an innovative approach to resolving the uniformity issue associated with large-area film fabrication.

Enhanced performance of solution-processed carbon nanotube transparent electrodes in foldable perovskite solar cells through vertical separation of binders by using eco-friendly parylene substrate

The successful utilization of an eco-friendly and biocompatible parylene-C substrate for high-performance solution-processed double-walled carbon nanotube(CNT)electrode-based perovskite solar cells(PSCs)was demonstrated.Through the use of a novel inversion transfer technique,vertical separation of the binders from the CNTs was induced,rendering a stronger p-doping effect and thereby a higher conductivity of the CNTs.The resulting foldable devices exhibited a power conversion efficiency of 18.11%,which is the highest reported among CNT transparent electrode-based PSCs to date,and withstood more than 10,000 folding cycles at a radius of 0.5 mm,demonstrating unprecedented mechanical stability.Furthermore,solar modules were fabricated using entirely laser scribing processes to assess the potential of the solution-processable nanocarbon electrode.Notably,this is the only one to be processed entirely by the laser scribing process and to be biocompatible as well as eco-friendly among the previously reported nonindium tin oxide-based perovskite solar modules.

Effect of drying methods on perovskite films and solar cells

The high efficiency,solution processibility,and flexibility of perovskite solar cells make them promising candidates for the photovoltaic industry[1−8].The deposition method is one of the most critical factors that affect the performance of perovskite films.Various deposition methods have been developed to make perovskite films,including spin-coating,slotdie coating.

Buried Interface Molecular Hybrid Enables Efficient Perovskite Solar Cells

Perovskite solar cells(PSCs)with a positive-intrinsicnegative(p–i–n,commonly referred to as“inverted”)structure are becoming commercially attractive due to their superior power conversion efficiency(PCE)and better operational stability as compared to the“normal”structure device.^([1–5])Nonetheless,further improvements in the device performance of inverted PSCs are hampered by interface losses,particularly where the buried interfaces are responsible for perovskite crystallization and chargecarrier extraction.^([6–9])

Accelerating the evaluation of operational lifetimes of perovskite solar cells and modules

Compared with the power conversion efficicency,the operational stability of perovskite solar cells(PsCs)remains a major challenge hampering its commercialization.However,conducting a light soaking test under 1 sun illumination to get a long lifetime is time-consuming and experimentally inefficient.Here,we report an accelerated stability test protocol by aging PsCs under high-intensity light illumination to accelerate the evaluation of their operation stability.It is found that the efficiency degradation rate of a typical inverted PsC is almost linearly dependent on the light intensity within the range of 1 to 4 suns regardless of the encapsulations.The results prove that it can save the light-soaking time by at least 4 times to predict the operation lifetime on the basis of the equivalent light irradiation dose.